Search Results (49)

The need to reduce greenhouse gas emissions and guarantee a stable and reliable energy supply has resulted in an increase in the demand for sustainable energy storage solutions over the last decade. Rechargeable batteries with solid-state electrolytes (SSE) have become a focus area due to their potential for increased energy density, longer cycle life, and safety over conventional liquid electrolytic batteries. The superionic sodium conductor (NASICON) Na₃Zr₂Si2PO₁₂ has gained a lot of attention among ESS because of its exceptional electrochemical properties, which make it a promising candidate for solid-state sodium-ion batteries. NASICON’s open frame structure makes it possible to transport sodium ions efficiently even at room temperature, while its wide electrochemical window enables high-voltage operation and reduces side reactions, resulting in safer battery performance. Furthermore, NASICON is more compatible with sodium ion systems, can help with electrode interface issues, and is simple to process. The characteristics of NASICON make it a highly desirable and vital material for solid-state sodium-ion batteries. The aim of this study is to prepare and characterize ceramic membranes that contain Na_3.06Zr₂Si₂PO₁₂ and Na_3.18Zr₂Si₂PO₁₂, and measure their stability in seawater batteries that serve as solid electrolytes. The surface analysis revealed that the Na_3.06Zr₂Si₂PO₁₂ powder has a specific surface area of 7.17 m² g⁻¹, which is more than the Na_3.18Zr₂Si₂PO₁₂ powder’s 6.61 m² g⁻¹. During measurement, the NASICON samples showed ionic conductivities of 8.5 × 10⁻⁵ and 6.19 × 10⁻⁴ S cm⁻¹. Using platinum/carbon (Pt/C) as a catalyst and seawater as a source of cathodes with sodium ions (Na⁺), batteries were charged and discharged using different current values (50 and 100 µA) for testing. In an electrochemical cell, a battery with a NASICON membrane and Pt/C catalysts with 0.00033 g platinum content was used to assess reproducibility at a constant current of 2 h. After 100 h of operation, charging and discharging voltage efficiency was 71% (50/100 µA) and 83.5% (100 µA). The electric power level is observed to increase with the number of operating cycles. Full article

Room-temperature all-solid-state sodium–sulfur (Na-S) batteries are being regarded as a promising technology for large-scale energy storage. However, the low ionic conductivity of existing sulfide solid electrolytes has been hindering the potential and commercialization of Na-S batteries. Na₃PS₄ has garnered extensive attention among sulfide solid electrolytes due to its potential ionic conductivity (primarily predominated by vacancies) and ease of fabrication. Herein, we demonstrated a combined melt-quenching with Br doping technique to pre-generate abundant defects (vacancies) in the Na₃PS₄, which expanded ion transport channels and facilitated Na⁺ migration. The quenched Na_2.9PS_3.9Br_0.1 holds an ionic conductivity of 8.28 × 10⁻⁴ S/cm at room temperature. Followed by the hot-pressed fabrication at 450 °C was conducted on the quenched Na_2.9PS_3.9Br_0.1 to reduce interface resistance, the resultant Na_2.9PS_3.9Br_0.1 pellet shows an ionic conductivity up to 1.15 × 10⁻³ S/cm with a wide electrochemical window and chemical stability towards Na alloy anodes. The assembled all-solid-state Na₂S/Na_2.9PS_3.9Br_0.1/Na₁₅Sn₄ cell delivers an initial reversible capacity of 550 mAh/g at a current density of 0.1 mA/cm². After 50 cycles, it still maintains 420 mAh/g with a capacity retention of 76.4%. The integration of melt-quenching, doping, and hot-pressing provides a new strategy to enable sulfide electrolytes with high ionic conductivity and all-solid-state Na-S batteries with high performance. Full article

Sodium–sulfur batteries have been provided as a highly attractive solution for large-scale energy storage, benefiting from their substantial storage capacity, the abundance of raw materials, and cost-effectiveness. Nevertheless, conventional sodium–sulfur batteries have been the subject of critique due to their high operating temperature and costly maintenance. In contrast, room-temperature sodium–sulfur batteries exhibit significant advantages in these regards. The most commonly utilized cathode active material is the S₈ molecule, whose intricate transformation process plays a crucial role in enhancing battery capacity. However, this process concomitantly generates a substantial quantity of polysulfide intermediates, leading to diminished kinetics and reduced cathode utilization efficiency. The pivotal strategy is the design of catalysts with adsorption and catalytic functionalities, which can be applied to the cathode. Herein, we present a summary of the current research progress in terms of nanostructure engineering, catalyst strategies, and regulating sulfur species conversion pathways from the perspective of high-performance host design strategy. A comprehensive analysis of the catalytic performance is provided from four perspectives: metal catalysts, compound catalysts, atomically dispersed catalysts, and heterojunctions. Finally, we analyze the bottlenecks and challenges, offering some thoughts and suggestions for overcoming these issues. Full article

Sodium–ion batteries are emerging as strong competition to lithium–ion batteries in certain market sections. While these cells do not use critical raw materials, they still feature a liquid electrolyte with all its inherent safety issues, like high flammability and toxicity. Alternative concepts like oxide-ceramic-based all-solid-state batteries feature the highest possible safety while still maintaining competitive electrochemical performance. However, production technologies are still in their infancy, especially for Na all-solid-state batteries, and need to be urgently developed to enable solid-state-battery technology using only abundant raw materials. In this study, the additive-free production of freestanding, undoped NaSICON separators via tape-casting is demonstrated, having an extremely high total Na-ion conductivity of up to 2.44 mS·cm⁻¹ at room temperature. Nevertheless, a strong influence of sample thickness on phase purity as well as electrochemical performance is uncovered. Additionally, the effect of self-coating of NaSICON during high-temperature treatment was evaluated as a function of thickness. While advantageous for increasing the stability against Na-metal anodes, detrimental consequences are identified when separator thickness is reduced to industrially relevant values and mitigation measures are postulated. Full article

Room-temperature sodium–sulfur (RT Na–S) batteries offer a superior, high-energy-density solution for rechargeable batteries using earth-abundant materials. However, conventional RT Na–S batteries typically use sulfur as the cathode, which suffers from severe volume expansion and requires pairing with a sodium metal anode, raising significant safety concerns. Utilizing Na₂S as the cathode material addresses these issues, yet challenges such as Na₂S’s low conductivity as well as the shuttle effect of polysulfide still hinder RT Na–S battery development. Herein, we present a simple and cost-effective method to fabricate a Na₂S–Na₆CoS₄/Co@C cathode, wherein Na₂S nanoparticles are embedded in a conductive carbon matrix and coupled with dual catalysts, Na₆CoS₄ and Co, generated via the in situ carbothermal reduction of Na₂SO₄ and CoSO₄. This approach creates a three-dimensional porous composite cathode structure that facilitates electrolyte infiltration and forms a continuous conductive network for efficient electron transport. The in situ formed Na₆CoS₄/Co electrocatalysts, tightly integrated with Na₂S, exhibit strong catalytic activity and robust physicochemical stabilization, thereby accelerating redox kinetics and mitigating the polysulfide shuttle effect. As a result, the Na₂S–Na₆CoS₄/Co@C cathode achieves superior capacity retention, demonstrating a discharge capacity of 346 mAh g⁻¹ after 100 cycles. This work highlights an effective strategy for enhancing Na₂S cathodes with embedded catalysts, leading to enhanced reaction kinetics and superior cycling stability. Full article

Due to its high thermal stability, environmental friendliness, and safety, lithium phosphate (Li₃PO₄) is used as a solid electrolyte in battery applications, but it is usually used with dopants due to its lower ionic conductivity, which is required for ion transport. However, due to its stability and environmentally friendly aspect, lithium phosphate is still a hot topic among suitable energy materials that need further research to improve its electrochemical properties. In the current work, a novel synthesis of lithium phosphate was proposed from the raw materials lithium carbonate (Li₂CO₃) and trisodium phosphate dodecahydrate (Na₃PO₄*12H₂O) under suitable stoichiometric conditions using the co-precipitation method. In the set of synthesized samples, a single-phase β-Li₃PO₄ (named LPO-4) with 99.7% purity and 93.49% yield was successfully prepared under appropriate stoichiometric conditions and pH 13 at 90 °C. The average particle size was 10 nm with a large surface area of 9.02 m²g⁻¹. Electrochemical impedance spectroscopy (EIS) of LPO-4 revealed a conductivity of 7.1 × 10⁻⁶ S.cm⁻¹ at room temperature and 2.7 × 10⁻⁵ S.cm⁻¹ at 80 °C with a low activation energy of 0.38 eV. This performance is attributed to the morphology of the nanotubes and the smaller particle size, which enlarge the reaction interfaces and shorten the diffusion distance of lithium ions. The kinetic and thermodynamic key parameters showed that the β-Li₃PO₄ exhibits thermal stability in the room temperature range up to 208.8 °C. All these property values indicate a promising application of lithium phosphate as a solid electrolyte in solid-state batteries and a new route for further investigation. Full article

Solid-state batteries offer significant advantages but present several challenges. Given the complexity of these systems, it is good practice to begin the study with simpler models and progressively advance to more complex configurations, all while maintaining an understanding of the physical principles governing solid-state battery operation. The results presented in this work pertain to cells without traditional electrodes, thus providing a foundation for guiding the development of fully functional solid-state cells. The open circuit voltage (OCV) of the Cu/Na_2.99Ba_0.005ClO composite in a cellulose/Zn pouch cell achieves 1.10 V, reflecting the difference in the chemical potentials of the current collectors (CCs), Zn and Cu, serving as electrodes. After 120 days, while set to discharge, conversely to what was expected, a higher potential difference of 1.13 V was attained (capacity of 5.9 mAh·g⁻¹_electrolyte). By incorporating a layer of carbon felt, the OCV became 0.85 V; however, after 95 days, the potential difference increased to 1.20 V. Ab initio simulations were additionally performed on a Cu/Na₃ClO/Zn heterojunction showing the formation of dipoles and the Na deposition on Zn which is demonstrated experimentally. The sodium plating on the negative CC (Zn) takes place as the cell is set to discharge at room temperature but is not observed at 40 °C. Full article

Currently, recycling of spent lithium-ion batteries is carried out using mechanical, pyrometallurgical and hydrometallurgical methods and their combination. The aim of this article is to study a part of the pyro-hydrometallurgical processing of spent lithium-ion batteries which includes lithium slag hydrometallurgical treatment and refining of the obtained leachate. Leaching was realized via dry digestion, which is an effective method capable of transferring over 99% of the present metals, such as Li, Al, Co, Cu, and others, to the leachate. In this work, the influence of three types of precipitation agents (NaOH, NH₄OH, Na₃PO₄) on the precipitation efficiency of Al and Li losses was investigated. It was found that the precipitation of aluminum with NaOH can result in the co-precipitation of lithium, causing total lithium losses up to 40%. As a suitable precipitating agent for complete Al removal from Li leachate with a minimal loss of lithium (less than 2%), crystalline Na₃PO₄ was determined under the following conditions: pH = 3, 400 rpm, 10 min, room temperature. Analysis confirmed that, in addition to aluminum, the precipitate also contains the REEs La (3.4%), Ce (2.5%), Y (1.3%), Nd (1%), and Pr (0.3%). The selective recovery of these elements will be the subject of further study. Full article

Sodium-ion batteries offer an attractive alternative to lithium-based chemistries due to the lower cost and abundance of sodium compared to lithium. Using solid electrolytes instead of liquid ones in such batteries may help improve safety and energy density, but they need to combine easy processing with high stability toward the electrodes. Herein, we describe a new class of solid electrolytes that are accessible by room-temperature, aqueous synthesis. The materials exhibit a garnet-type zinc hexacyanoferrate framework with large diffusion channels for alkaline ions. Specifically, they show superionic behavior and allow for facile processing into pellets. We compare the structure, stability, and transport properties of lithium-, sodium-, and potassium-containing zinc hexacyanoferrates and find that Na₂Zn₃[Fe(CN)₆]₂ achieves the highest ionic conductivity of up to 0.21 mS/cm at room temperature. In addition, the electrochemical performance and stability of the latter solid electrolyte are examined in solid-state sodium-ion batteries. Full article

The solid-state metal battery with solid-state electrolytes has been considered the next generation of energy storage technology owing to its superior safety and high energy density. But, unfavorable ionic conductivity and interfacial problems make it difficult to widely use in practice. In this work, Si₃N₄ was rationally introduced into the NASICON matrix as a sintering aid, and the influence of Si₃N₄ on the crystal phase, microstructure, electrochemical and electrical performance of Na₃Zr₂Si₂PO₁₂ (NZSP) ceramic was systematically studied. The results demonstrate that the introduction of Si₃N₄ can effectively lower the densification sintering temperature of Na₃Zr₂Si₂PO₁₂ electrolyte and enhance the room temperature ionic conductivity of the NZSP to 3.82 × 10⁻⁴ S cm⁻¹. In addition, since Si₃N₄ has a high thermal conductivity and can inhibit the transmission of electrons between the grains of the electrolyte matrix, it will effectively hinder the generation of sodium metal dendrites and relieve the concentration of the heat source. Moreover, owing to the desirable interface compatibility of the Na and NZSP-Si₃N₄ electrolyte, the Na/NZSP-1150-1%Si₃N₄/Na symmetric battery exhibits excellent stability, and the electrode/electrolyte interface still maintains good integrity even after long-term cycling. The assembled Na/NZSP-1150-1%Si₃N₄/Na_3.5V_0.5Mn_0.5Fe_0.5Ti_0.5(PO₄)₃ cell manifests an initial specific capacity of 152.5 mA h g⁻¹, together with an initial Coulombic efficiency of 99.8%. Furthermore, after 200 cycles, the battery displays a capacity retention rate of 82%. Full article

A new approach to developing structural sodium batteries capable of operating in ambient-temperature conditions has been successfully achieved. The developed multifunctional structural electrolyte (SE) using poly(ethylene oxide) (PEO) as a matrix integrated with succinonitrile (SN) plasticizers and glass-fiber (GF) reinforcements identified as GF_PEO-SN-NaClO₄ showed a tensile strength of 32.1 MPa and an ionic conductivity of 1.01 × 10⁻⁴ S cm⁻¹ at room temperature. It displayed a wide electrochemical stability window of 0 to 4.9 V and a high sodium-ion transference number of 0.51 at room temperature. The structural electrode (CF|SE) was fabricated by pressing the structural electrolyte with carbon fibers (CFs), and it showed a tensile strength of 72.3 MPa. The fabricated structural battery half-cell (CF||SE||Na) demonstrated good cycling stability and an energy density of 14.2 Wh kg⁻¹, and it retained 80% capacity at the end of the 200th cycle. The cycled electrodes were observed using scanning electron microscopy, which revealed small dendrite formation and dense albeit uniform deposition of the sodium metal, helping to avoid a short-circuit of the cell and providing more cycling stability. The developed multifunctional matrix composites demonstrate promising potential for developing ambient-temperature sodium structural batteries. Full article

Prussian blue analogs (PBAs) are appealing cathode materials for sodium-ion batteries because of their low material cost, facile synthesis methods, rigid open framework, and high theoretical capacity. However, the poor electrical conductivity, unavoidable presence of [Fe(CN)₆] vacancies and crystalline water within the framework, and phase transition during charge–discharge result in inferior electrochemical performance, particularly in terms of rate capability and cycling stability. Here, cobalt-free PBAs are synthesized using a facile and economic co-precipitation method at room temperature, and their sodium-ion storage performance is boosted due to the reduced crystalline water content and improved electrical conductivity via the high-entropy and component stoichiometry tuning strategies, leading to enhanced initial Coulombic efficiency (ICE), specific capacity, cycling stability, and rate capability. The optimized HE-HCF of Fe_0.60Mn_0.10-hexacyanoferrate (referred to as Fe_0.60Mn_0.10-HCF), with the chemical formula Na_1.156Fe_0.599Mn_0.095Ni_0.092Cu_0.109Zn_0.105 [Fe(CN)₆]_0.724·3.11H₂O, displays the most appealing electrochemical performance of an ICE of 100%, a specific capacity of around 115 and 90 mAh·g⁻¹ at 0.1 and 1.0 A·g⁻¹, with 66.7% capacity retention observed after 1000 cycles and around 61.4% capacity retention with a 40-fold increase in specific current. We expect that our findings could provide reference strategies for the design of SIB cathode materials with superior electrochemical performance. Full article

In the pursuit of high energy density batteries beyond lithium, room-temperature (RT) sodium–sulfur (Na-S) batteries are studied, combining sulfur, as a high energy density active cathode material and a sodium anode considered to offer high energy density and very good standard potential. Different liquid electrolyte systems, including three different salts and two different solvents, are investigated in RT Na-S battery cells, on the basis of the solubility of sulfur and sulfides, specific capacity, and cyclability of the cells at different C-rates. Two alternative cathode host materials are explored: A bimodal pore size distribution activated carbon host AC MSC30 and a highly conductive carbon host of hollow particles with porous particle walls. An Na-S cell with a cathode coating with 44 wt% sulfur in the AC MSC30 host and the electrolyte 1M NaFSI in DOL/DME exhibited a specific capacity of 435 mAh/g_S but poor cyclability. An Na-S cell with a cathode coating with 44 wt% sulfur in the host of hollow porous particles and the electrolyte 1M NaTFSI in TEGDME exhibited a specific capacity of 688 mAh/g_S. Full article

The global environmental crisis necessitates reliable, sustainable, and safe energy storage solutions. The current systems are nearing their capacity limits due to the reliance on conventional liquid electrolytes, which are fraught with stability and safety concerns, prompting the exploration of solid-state electrolytes, which enable the integration of metal electrodes. Solid-state sodium-ion batteries emerge as an appealing option by leveraging the abundance, low cost, and sustainability of sodium. However, low ionic conductivity and high interfacial resistance currently prevent their widespread adoption. This study explores polyvinyl-based polymers as wetting agents for the NASICON-type NZSP (Na₃Zr₂Si₂PO₁₂) solid electrolyte, resulting in a combined system with enhanced ionic conductivity suitable for Na-ion solid-state full cells. Electrochemical impedance spectroscopy (EIS) performed on symmetric cells employing NZSP paired with different wetting agent compositions demonstrates a significant reduction in interfacial resistance with the use of poly(vinyl acetate)—(PVAc-) based polymers, achieving an impressive ionic conductivity of 1.31 mS cm⁻¹ at room temperature, 63.8% higher than the pristine material, notably reaching 7.36 mS cm⁻¹ at 90 °C. These results offer valuable insights into the potential of PVAc-based polymers for advancing high-performance solid-state sodium-ion batteries by reducing their total internal resistance. Full article

Sodium- (Na⁺) and potassium- (K⁺) ion batteries are cost-effective alternatives to lithium-ion (Li⁺) batteries due to the abundant sodium and potassium resources. Solid polymer electrolytes (SPEs) are essential for safer and more efficient Na⁺ and K⁺ batteries because they often exhibit low ionic conductivity at room temperature. While zwitterionic (ZW) materials enhance Li⁺ battery conductivity, their potential for Na⁺ and K⁺ transport in batteries remains unexplored. In this study, we investigated the effect of three ZW molecules (ChoPO4, i.e., 2-methacryloyloxyethyl phosphorylcholine, ImSO3, i.e., sulfobetaine ethylimidazole, and ImCO2, i.e., carboxybetaine ethylimidazole) on the dissociation of Na⁺ and K⁺ coordination with ethylene oxide (EO) chains in EO-based electrolytes through molecular dynamics simulations. Our results showed that ChoPO4 possessed the highest cation–EO₁₀ dissociation ability, while ImSO3 exhibited the lowest. Such dissociation ability correlated with the cation–ZW molecule coordination strength: ChoPO4 and ImSO3 showed the strongest and the weakest coordination with cations. However, the cation–ZW molecule coordination could slow the cationic diffusion. The competition of these effects resulted in accelerating or decelerating cationic diffusion. Our simulated results showed that ImCO2 enhanced Na⁺ diffusion by 20%, while ChoPO4 and ImSO3 led to a 10% reduction. For K⁺, ChoPO4 reduced its diffusion by 40%, while ImCO2 and ImSO3 caused a similar decrease of 15%. These findings suggest that the ZW structure and the cationic size play an important role in the ionic dissociation effect of ZW materials. Full article